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United States Patent |
6,054,533
|
Farkas
,   et al.
|
April 25, 2000
|
Compatibilized blends of a thermoplastic elastomer and a polyolefin
Abstract
A compatibilized blend of a thermoplastic elastomer and a polyolefin. The
compatibilizer is a thermoplastic polyurethane formed by the reaction of a
substantially hydrocarbon intermediate such as a polybutadiene polyol, a
diisocyanate such as MDI, and an amine or diol chain extender such as
neopentyl glycol. The compatibilizer has high amounts of soft segments
therein and imparts improved properties to blends of a thermoplastic
elastomer and polyolefin such as good impact resistance, good tensile
strength, good tear resistance, and good delamination resistance.
Inventors:
|
Farkas; Julius (North Ridgeville, OH);
Jacobs; Charles Patrick (Elyria, OH);
Lawson; Dennis Lee (Brunswick, OH);
Wilson; Gary Franklin (Grafton, OH)
|
Assignee:
|
The B.F. Goodrich Company (Richfield, OH)
|
Appl. No.:
|
951013 |
Filed:
|
October 15, 1997 |
Current U.S. Class: |
525/90; 525/89; 525/92A; 525/125; 525/128; 525/130 |
Intern'l Class: |
C08L 023/12; C08L 075/04 |
Field of Search: |
525/89,90,92 A,125,128,130
|
References Cited
U.S. Patent Documents
5242977 | Sep., 1993 | Franke | 525/125.
|
5358981 | Oct., 1994 | Southwick.
| |
5393843 | Feb., 1995 | Handlin, Jr. et al.
| |
5405911 | Apr., 1995 | Handlin, Jr. et al.
| |
5486570 | Jan., 1996 | St. Clair.
| |
5576388 | Nov., 1996 | St. Clair et al.
| |
5589543 | Dec., 1996 | Yokelson et al.
| |
5605961 | Feb., 1997 | Lee et al.
| |
Foreign Patent Documents |
0131714 | Jan., 1985 | EP.
| |
657502 | Jun., 1995 | EP.
| |
0641828 | Aug., 1995 | EP.
| |
0732 349 A2 | Sep., 1996 | EP.
| |
4-25566 | Jan., 1992 | JP.
| |
WO 97/00901 | Jan., 1997 | WO.
| |
Primary Examiner: Buttner; David
Attorney, Agent or Firm: Dureska; David P., Hudak; Daniel J.
Claims
What is claimed is:
1. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin, comprising steps of:
heating the thermoplastic elastomer and polyolefin in the presence of a
compabilizing agent to a temperature above the melting point of said
thermoplastic elastomer and said polyolefin; and
mixing the heated thermoplastic elastomer, polyoletin, and compatibilizing
agent to form a blend;
wherein said compatibilizing agent is a thermoplastic polyurethane derived
from a reaction of a diisocyanate, a chain extender, and a hydrocarbon
polymer having a number average molecular weight of not greater than
10,000 and having isocyanate-reactive functional groups, wherein said
hydrocarbon polymer contains a solely hydrocarbon chain between said
functional groups, wherein said hydrocarbon polymer is derived from one or
more dienes having a total of from 4 to 8 carbon atoms, and wherein said
hydrocarbon polymer has isocyanate-reactive functional groups selected
from a group consisting of amines and hydroxyls: wherein said chain
extender is selected from a group consisting of diamines, alkanolamines,
and diols, wherein said diols have a total of from 2 to 15 carbon atoms;
wherein the compatibilizing agent has hard segments and soft segments,
wherein the compatibilizing agent is at least 25 percent by weight based
upon the total weight of the compatibilizing agent soft segments, and
wherein said hard segments result from reactions of the diisocyanate and
the isocyanate-reactive functional groups or from reactions of the
diisocyanate and the chain extender.
2. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 1, wherein the amount of
said thermoplastic elastomer is from about 5 percent to about 95 percent
by weight and wherein the amount of said polyolefin is from about 95 to
about 5 percent by weight based upon the total weight of said
thermoplastic elastomer and said polyolefin, and
wherein the amount of said compatibilizing agent is from about 0.25 to
about 15 parts by weight per 100 parts by total weight of said
thermoplastic elastomer and said polyolefin.
3. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 1, wherein said
thermoplastic elastomer is selected from a group consisting of a
thermoplastic polyester elastomer, a thermoplastic polyamide elastomer, a
thermoplastic urethane polymer, or combinations thereof, and wherein said
diisocyanate has a total of from about 2 to about 30 carbon atoms.
4. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 1, wherein said
thermoplastic elastomer has a weight average molecular weight of from
about 20,000 to about 500,000, wherein said polyolefin has a weight
average molecular weight of from about 40,000 to about 2,000,000 and
wherein the molar ratio of isocyanate groups of said diisocyanate to
isocyanate-reactive functional groups of the chain extender and the
hydrocarbon polymer is from about 0.80 to about 1.05.
5. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 1, wherein the amount of
said polyolefin is from about 85 percent to about 40 percent by weight of
the total weight of the polyolefin and the thermoplastic elastomer and
wherein the amount of said thermoplastic elastomer is from about 15 to
about 60 percent by weight of the total weight of the polyolefin and the
thermoplastic elastomer, and wherein said compatibilizing agent contains
from about 45 to about 90 percent by weight soft segments.
6. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 1, wherein said mixing is
performed at a temperature from about 180.degree. C. to about 240.degree.
C., and wherein said hydrocarbon polymer is derived from butadiene.
7. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 1, wherein said
thermoplastic elastomer is a urethane polymer, wherein the amount of said
compatibilizing agent is from about 0.5 to about 6 parts by weight for
every 100 parts by total weight of the thermoplastic elastomer and the
polyolefin, wherein said diisocyanate is methylene
bis-(4-phenylisocyanate), wherein said chain extender is selected from a
group consisting of 2-butyl-2-ethyl-1,3-propane diol, neopentyl glycol,
and combinations thereof, wherein the molar ratio of said isocyanate
groups to the isocyanate-reactive functional groups of the chain extender
and the hydrocarbon polymer is about 0.9 to about 1.01, wherein said
polyolefin is polypropylene, and wherein said hydrocarbon polymer is
derived from butadiene.
8. A compatibilized blend of a thermoplastic elastomer and a polyolefin,
comprising:
from about 5 to about 95 percent by weight of the thermoplastic elastomer
and from about 95 to about 5 percent by weight of the polyolefin based
upon the total weight of said thermoplastic elastomer and said polyolefin,
and
an effective amount of a compatibilizing agent to compatibilize said
thermoplastic elastomer and said polyolefin, said compatibilizing agent
being a thermoplastic polyurethane derived from a reaction of a
diisocyanate, a chain extender, and a hydrocarbon polymer having a number
average molecular weight of not greater than 10,000 and having
isocyanate-reactive functional groups, wherein said hydrocarbon polymer
contains a solely hydrocarbon chain between said functional groups,
wherein said hydrocarbon polymer is derived from one or more dienes having
a total of from 4 to 8 carbon atoms, and wherein said hydrocarbon polymer
has isocyanate-reactive functional groups selected from a group consisting
of hydroxyls and amines; wherein said chain extender is selected from a
group consisting of diamines, alkanolamines, and diols, wherein said diols
have a total of from 2 to 15 carbon atoms; wherein the compalibilizing
agent has hard segments and soft segments, wherein the compatibilizing
agent is at least 25 percent by weight based upon the total weight of the
compatibilizing agent soft segments, and wherein said hard segments result
from reactions of the diisocyanate and the isocyanate-reactive functional
groups or from reactions of the diisoyanate and the chain extender.
9. A compatibilized blend according to claim 8, wherein the molar ratio of
isocyanate groups of said diisocyanate to the isocyanate-reactive
functional groups of said chain extender and said hydrocarbon polymer is
from about 0.8 to about 1.05.
10. A compatibilized blend according to claim 8, wherein an effective
amount of said compatibilizing agent is from about 0.25 to about 15 parts
by weight per 100 parts by total weight of said thermoplastic elastomer
and said polyolefin, and wherein said compatibilizing agent is at least 35
percent by weight based upon the total weight of the compatibilizing agent
soft segments.
11. A compatibilized blend according to claim 8, wherein said thermoplastic
elastomer is selected from a group consisting of a thermoplastic polyester
elastomer, a thermoplastic polyamide elastomer, and a thermoplastic
urethane polymer, wherein said urethane polymer is derived from a
polyester polyol, a polyether polyol, or combinations thereof; and wherein
said polyolefin is polypropylene.
12. A compatibilized blend according to claim 8, wherein said diisocyanate
is methylene bis-(4-phenylisocyanate), and wherein said chain extender is
selected from a group consisting of neopentyl glycol,
2-butyl-2-ethyl-1,3-propane diol, and combinations thereof.
13. A compatibilized blend according to claim 1, wherein the thermoplastic
elastomer is a urethane polymer and said urethane polymer is present in an
amount from about 15 to about 60 percent by weight based upon the total
weight of said thermoplastic elastomer and said polyolefin; wherein the
polvolefin is polypropylene, and said polyolefin is present in an amount
of from about 40 to about 85 percent by weight based upon the total weight
of said thermoplastic elastomer and said polyolefin, and wherein the
amount of said compatibilizing agent is from about 0.50 part to about 6
parts by weight, and wherein said molar ratio of said isocyanate groups of
said diisocyanate to said isocyanate-reactive functional groups is from
about 0.9 to about 1.01.
14. A compatibilized blend according to claim 8, wherein said thermoplastic
elastomer is a thermoplastic urethane polymer and is present in an amount
of from about 15 to about 60 percent by weight based upon the total weight
of said thermoplastic elastomer and said polyolefin, wherein said
polyolefin is polypropylene and is present in an amount of from about 40
percent to about 85 percent by weight based upon the total weight of said
thermoplastic elastomer and said polyolefin; and wherein said
compatibilizing agent has from about 45 to about 90 percent by weight of
the compatibilizinp agent of soft segments, and wherein the
compatibilizing, agent is present in an amount of from about 0.5 to about
6 parts by weight for every 100 parts by total weight of the thermoplastic
elastomer and the polyolefin, wherein the diisocyanate is methylene
bis-(4-phenylisocyanate), and wherein the chain extender is selected from
a group consisting of 2-butyl-2-ethyl-1,3-propane diol, neopentyl plycol,
and combinations thereof; and wherein the molar ratio of said isocyanate
groups to the isocyanate-reactive functional groups of the chain extender
and the hydrocarbon polymer is about 0.9 to about 1.01; and wherein said
hydrocarbon polymer is derived from butadiene.
15. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin, comprising steps of:
heating the thermoplastic elastomer and polyolefin in the presence of at
compatibilizing agent a temperature above the melting point of said
thermoplastic elastomer and said polyolefin; and
mixing said heated thermoplastic elastomer polyolefin, and compatibilizing
agent to form a blend;
wherein said compatibilizing agent is a thermoplastic polyurethane derived
from a reaction of a diisocyanate, a chain extender, and a polymer having
isocyanate-reactive functional groups selected from a group consisting of
hydroxyls and amines therein and having at least 20 consecutive carbon
atoms in its backbone chain between any non-carbon atoms and a number
average molecular weight of not greater than 10,000; wherein the chain
extender is selected from a group consisting of diamines, alkanolamines,
and diols, wherein said diols have a total of from 2 to 15 carbon atoms;
wherein the compatibilizing agent has hard segments and soft segments;
wherein the compatibilizing agent is at least 25 percent by weight based
upon the total weight of the compatibilizing agent soft segments, and
wherein said hard segments result from reactions of the diisocyanate and
the isocyanate-reactive functional groups or from reactions of the
diisocyanate and the chain extender.
16. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 15, wherein the amount of
said thermoplastic elastomer is from about 5 percent to about 95 percent
by weight based upon the total weight of said thermoplastic elastomer and
said polyolefin, wherein the amount of said polyolefin is from about 95
percent by weight to about 5 percent by weight based upon the total weight
of said thermoplastic elastomer and said polyolefin, and wherein the
amount of said compatibilizing agent is from about 0.25 to about 15 parts
by weight per 100 parts by weight based upon the total weight of said
thermoplastic elastomer and said polyolefin.
17. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 15, wherein said
thermoplastic elastomer is selected from a group consisting of a
thermoplastic polyester elastomer, a thermoplastic polyamide elastomer, a
thermoplastic urethane polymer, and combinations thereof and wherein said
diisocyanate has a total of from about 2 to about 30 carbon atoms.
18. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 15, wherein said
thermoplastic elastomer has a weight average molecular weight of from
about 20,000 to about 500,000, wherein said polyolefin has a weight
average molecular weight of from about 40,000 to about 2,000,000; wherein
the polymer having isocyanate-reactive functional groups therein has at
least 30 consecutive carbon atoms in its backbone chain between any
non-carbon atoms; and wherein the molar ratio of isocyanate groups of said
diisocyanate to isocyanate-reactive functional groups of the chain
extender and the polymer is from about 0.80 to about 1.05.
19. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 15, wherein the amount of
said polyolefin is from about 85 percent to about 40 percent by weight of
the total weight of the polyolefin and the thermoplastic elastomer and
wherein the amount of said thermoplastic elastomer is from about 15 to
about 60 percent by weight of the total weight of the polyolefin and the
thermoplastic elastomer, and wherein said compatibilizing agent contains
from about 45 to about 90 percent by weight soft segments.
20. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 15, wherein said mixing is
performed at a temperature from about 180.degree. C. to about 240.degree.
C., and wherein said polymer having isocyanate-reactive functional groups
therein is a dimerdiol having at least 36 consecutive carbon atoms between
any non-carbon atoms in its backbone chain.
21. A process for forming a compatibilized blend of a thermoplastic
elastomer and a polyolefin according to claim 15, wherein said
thermoplastic elastomer is a urethane polymer and said thermoplastic
elastomer is present in an amount of about 15 percent by weight to about
60 percent by weight based upon the total weight of the thermoplastic
elastomer and the polyolefin; wherein said polyolefin is polypropylene and
said polyolefin is present in an amount of about 85 percent by weight to
about 40 percent by weight based upon the total weight of the
thermoplastic elastomer and the polyolefin; and wherein the amount of said
compatibilizing agent is from about 0.5 to about 6 parts by weight for
every 100 parts by total weight of the thermoplastic elastomer and the
polyolefin, wherein said diisocyanate is methylene
bis-(4-phenylisocyanate), wherein said chain extender is selected from a
group consisting of 2-butyl-2-ethyl-1,3-propane diol, neopentyl glycol,
and combinations thereof, wherein the molar ratio of said isocyanate
groups to the isocyanate-reactive functional groups of the chain extender
and the polymer having isocyanate-reactive functional groups therein is
about 0.9 to about 1.01, and wherein the polymer having
isocyanate-reactive functional groups therein is a dimerdiol dimerate
prepared from a dimerdiol having at least 36 consecutive carbon atoms in
its backbone chain between any non-carbon atoms and a dimer acid having at
least 44 carbon atoms in its backbone chain between any non-carbon atoms.
22. A compatibilized blend of a thermoplastic elastomer and a polyolefin,
comprising:
from about 5 to about 95 percent by weight of the thermoplastic elastomer
and from about 95 percent to about 5 percent by weight of the polyolefin
based upon the total weight of said thermoplastic elastomer and said
polyolefin, and
an effective amount of a compatibilizing agent to compatibilize said
thermoplastic elastomer and said polyolefin, said compatibilizing agent
being a thermoplastic polyurethane derived from a reaction of a
diisocyanate, a chain extender, and a polymer having isocyanate-reactive
functional groups selected from a group consisting of hydroxyls and amines
therein and having at least 20 consecutive carbon atoms in its backbone
chain between any non-carbon atoms and a number average molecular weight
of not greater than 10,000; wherein the chain extender is selected from a
group consisting of diamines, alkanolamines, and diols, wherein said diols
have a total of from 2 to 15 carbon atoms; wherein the compatibilizing
agent has hard segments and soft segments; wherein the compatibilizing
agent is at least 25 percent by weight based upon the total weight of the
compatibilizing agent soft segments, and wherein said hard segments result
from reactions of the diisocyanate and the isocyanate-reactive functional
groups or from reactions of the diisocyanate and the chain extender.
23. A compatibilized blend according to claim 22, wherein the molar ratio
of isocyanate groups of said diisocyanate to the isocyanate-reactive
functional groups of said chain extender and said polymer having
isocyanate-reactive functional groups therein is from about 0.8 to about
1.05.
24. A compatibilized blend according to claim 22, wherein an effective
amount of said compatibilizing agent is from about 0.25 to about 15 parts
by weight per 100 parts by total weight of said thermoplastic elastomer
and said polyolefin, and wherein said compatibilizing agent is at least 35
percent by weight based upon the total weight of the compatibilizing agent
soft segments.
25. A compatibilized blend according to claim 22, wherein said
thermoplastic elastomer is selected from a group consisting of a
thermoplastic polyester elastomer, a thermoplastic polyamide elastomer,
and a thermoplastic urethane polymer, wherein said urethane polymer is
derived from a polyester polyol, a polyether polyol, or combinations
thereof, and wherein said polyolefin is polypropylene.
26. A compatibilized blend according to claim 22, wherein said diisocyanate
is methylene bis-(4-phenylisocyanate), and wherein said chain extender is
selected from a group consisting of neopentyl glycol,
2-butyl-2-ethyl-1,3-propane diol, and combinations thereof.
27. A compatibilized blend according to claim 22, wherein the thermoplastic
elastomer is a urethane polymer and said urethane polymer is present in an
amount from about 15 to about 60 percent by weight based upon the total
weight of said thermoplastic elastomer and said polyolefin; wherein the
polyolefin is polypropylene, and said polyolefin is present in an amount
of from about 40 percent to about 85 percent by weight based upon the
total weight of said thermoplastic elastomer and said polyolefin, and
wherein the amount of said compatibilizing agent is from about 0.50 part
to about 6 parts by weight, and wherein said molar ratio of said
isocyanate groups of said diisocyanate to said isocyanate-reactive
functional groups is from about 0.9 to about 1.01.
28. A compatibilized blend according to claim 22, wherein said
thermoplastic elastomer is a thermoplastic urethane polymer and is present
in an amount of from about 15 to about 60 percent by weight based upon the
total weight of said thermoplastic elastomer and said polyolefin, wherein
said polyolefin is polypropylene and is present in an amount of from about
40 percent to about 85 percent by weight based upon the total weight of
said thermoplastic elastomer and said polyolefin; and wherein said
compatibilizing agent has from about 45 percent to about 90 percent by
weight of the compatibilizing agent soft segments, and wherein the
compatibilizing agent is present in an amount of from about 0.5 part to
about 6 parts by weight for every 100 parts by total weight of the
thermoplastic elastomer and the polyolefin, wherein the diisocyanate is
methylene bis-(4-phenylisocyanate), and wherein the chain extender is
selected from a group consisting of 2-butyl-2-ethyl-1,3-propane diol,
neopentyl glycol, and combinations thereof; and wherein the molar ratio of
said isocyanate groups to the isocyanate-reactive functional groups of the
chain extender and the polymer having isocyanate-reactive functional
groups therein is about 0.9 to about 1.01; and wherein said polymer having
isocyanate-reactive functional groups therein is a dimerdiol dimerate
prepared from a dimerdiol containing at least 36 carbon atoms and a timer
acid containing about 44 carbon atoms.
Description
FIELD OF INVENTION
The present invention relates to compatibilizing blends of a polyolefin
such as polypropylene with a thermoplastic elastomer such as a urethane
polymer, e.g., made from a polyester or polyether polyol. The present
invention also relates to a polyurethane compatibilizing agent for the
blend which agent contains a majority amount of soft segments therein and
which is derived from a substantially hydrocarbon intermediate such as a
polydiene diol.
BACKGROUND OF THE INVENTION
Heretofore, various types of polyurethanes have been made from polyester or
polyether polyols. Such thermoplastic polyurethanes are generally
incompatible with polyolefins such as polypropylene.
U.S. Pat. No. 5,589,543, to Yokelson et al., relates to hydrophobic
polyurethane elastomers containing a linear soft segment without pendant
chain-branched groups, wherein said polyurethane elastomer has a glass
transition temperature (Tg) of less than -70.degree. C., and a moisture
uptake of less than 1.0 wt. % after 24 hours of immersion in water at
70.degree. C., and wherein said polyurethane elastomer comprises at least
one repeat unit containing said linear soft segment, which soft segment
comprises a moiety derived from a polyol which is an unsaturated
hydrocarbon polyol.
PCT International Application Publication No. WO 97/00901, to Cenens,
relates to a thermoplastic polyurethane formed from a polydiene diol,
preferably a hydrogenated polybutadiene diol, having from 1.6 to 2
terminal hydroxyl groups per molecule and a number average molecular
weight between 500 and 20,000, an isocyanate having two isocyanate groups
per molecule, and optionally a chain extender having two hydroxyl groups
per molecule. The thermoplastic polyurethane composition is prepared by a
prepolymer method, preferably a solventless prepolymer method using a
branched chain extender.
European Patent Application No. EP 0 732 349, to Kaufhold, relates to a
thermoplastic polyurethane resin prepared by reacting an isocyanate, a
polyol, a reactive polyolefin, and a chain extender. The resin is blended
with polypropylene.
SUMMARY OF THE INVENTION
Polyolefins are blended with thermoplastic elastomers such as thermoplastic
polyester elastomers, thermoplastic polyamide elastomers, or thermoplastic
urethane polymers such as those derived from polyester and/or polyether
polyols, through the use of a urethane compatibilizing agent. The
compatibilizer is made by melt-polymerizing a substantially hydrocarbon
intermediate such as that derived from various saturated or unsaturated
polydienes, for example polybutadiene, a diisocyanate, and desirably chain
extender. The amount of the hydrocarbon intermediate is large such that
the compatibilizer contains at least 55 percent by weight of soft segments
therein.
DETAILED DESCRIPTION OF THE INVENTION
The compatibilizer is a thermoplastic polyurethane derived from the
reaction of a substantially hydrocarbon intermediate, a diisocyanate, and
a chain extender. The hydrocarbon intermediate is a low molecular weight
compound or a polymer having hydroxyl (preferred), amine, or carboxylic
acid terminal groups thereon. When the substantially hydrocarbon
intermediate is not solely a hydrocarbon but, e.g., a polyester, the
number of consecutive polymer backbone carbon atoms between a non-carbon
atom such as oxygen, is large, i.e., at least 20 carbon atoms, desirably
at least 30 carbon atoms, and preferably at least 45 carbon atoms. An
example of such a substantially hydrocarbon intermediate, i.e., a long
chain polyester polyol Priplast 3197 from Unichema. Priplast 3197 is a
dimerdiol dimerate prepared from dimerdiol Pripol 2033 containing at least
36 carbon atoms and a dimer acid containing about 44 carbon atoms. A
suitable low molecular weight hydrocarbon intermediate is Pripol 2033 from
Unichema, a 36 carbon atom dimerdiol. However, the intermediate is
preferably solely a hydrocarbon intermediate derived from one or more
dienes having a total of from 4 to 8 carbon atoms, such as butadiene,
isoprene, and the like, with butadiene being preferred. The number average
molecular weight of the hydrocarbon intermediate is generally from about
300 or 500 to about 10,000, desirably from about 1,000 to about 7,500, and
preferably from about 2,000 to about 5,000. The hydrocarbon intermediate
can be unsaturated but preferably is substantially hydrogenated such that
at least 80 percent, desirably 90 or 95 percent, and preferably at least
98 percent, 99 percent, and even 100 percent of the carbon-carbon double
bonds in the intermediate are saturated. Hydrogenation may be carried out
according to any conventional process or manner such as set forth in U.S.
Pat. Nos. 5,393,843 or 5,405,911, hereby fully incorporated by reference.
When butadiene is utilized, the microstructure of the resulting polymer
can be largely 1,2 structure or 1,4 structure (e.g., 15 to 85%) with a
similar amount (e.g., 35 to 65%) of each generally being preferred.
Examples of hydrocarbon polyols derived from butadiene include the
following:
______________________________________
Identification
Supplier Description
______________________________________
Kraton Liquid
Shell Hydroxyl-terminated polybutadiene,
L2203 hydrogenated. Approximate micro-
structure: 55% 1,2; 45% 1,4.
Polytail H Mitsubishi Hydroxyl-terminated polybutadiene,
hydrogenated. Approximate micro-
structure: 21% 1,2; 79% 1,4.
Polytail HA Mitsubishi Hydroxyl-terminated polybutadiene,
hydrogenated. Approximate micro-
structure: 83% 1,2; 17% 1,4.
Krasol LBH Kaucuk AG Hydroxyl-terminated polybutadiene.
Approximate microstructure: 65% 1,2;
35% 1,4.
Liquiflex H Petroflex Hydroxyl-terminated polybutadiene.
Approximate microstructure: 22% 1,2;
78% 1,4.
______________________________________
Kraton L2203 is preferred in the present invention.
The term "polyol" with respect to a substantially hydrocarbon polyol
intermediate is to be understood to mean that while preferably the
hydrocarbon has two functional hydroxyl end groups, the same can generally
range from about 1.8 to about 2.2 end groups per molecule.
The isocyanates utilized in the present invention are preferably
diisocyanates and include aliphatic, cycloaliphatic, aromatic,
alkyl-substituted aromatic diisocyanates and the like, as well as mixtures
thereof. Such diisocyanates generally contain a total of from abut 2 to
about 30 carbon atoms, and representative examples include ethylene
diisocyanate; toluene diisocyanate; methylene bis-(4-phenylisocyanate),
that is, MDI; isophorone diisocyanate; hexamethylene diisocyanate;
naphthalene diisocyanate; cyclohexylene diisocyanate; diphenylmethane-3,3'
dimethoxy-4,4'-diisocyanate, meta-tetramethylxylene diisocyanate
(m-TMXD1), paratetramethylxylene diisocyanate (p-TMXD1), m-xylylene
diisocyanate (XDI), decane-1,10-diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, as well as combinations thereof,
and the like, with MDI being preferred. It is to be understood that
isomers of the various diisocyanate can also be used.
The chain extenders can be either diamines, alkanolamines, or preferably
diols containing a total of from 2 to 15 carbon atoms. Examples of chain
extenders include ethanolamine, ethylene diamine, ethylene glycol,
1,3-propane diol, 2,3- or 1,4-butane diol, 1,5-pentane diol, 1,6-hexane
diol, hydroquinone bis(2-hydroxyethyl)ether, 1,4-cyclohexanediol,
diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, and the
like, with 2-butyl-2-ethyl-1,3-propane diol (BEPD) being preferred, and
neopentyl glycol being highly preferred. The amount of the chain extender
can be zero (i.e., none) but desirably is from about 3 to about 30 percent
by weight and preferably from about 6 to about 25 percent by weight based
upon the total weight of chain extender and the substantially hydrocarbon
intermediate utilized in the formation of the thermoplastic polyurethane
compatibilizer. The amount of the chain extender and intermediate
utilized, whether they contain hydroxyl groups, amine groups, etc., is
generally an equivalent excess to the amount of diisocyanate utilized.
That is, the molar ratio of the diisocyanate to hydrocarbon intermediate
and chain extender is generally from about 0.8 to about 1.05 and desirably
from about 0.9 to about 1.01.
It is a desirable aspect of the present invention to make the thermoplastic
polyurethane compatibilizer by either the random polymerization method
wherein the substantially hydrocarbon intermediate, the diisocyanate and
the chain extender are all added tocether at once and polymerized, or by
the prepolymer method. The prepolymer method is preferred where the chain
extender is not soluble in the intermediate as generally is the case.
Thus, the prepolymer method is generally preferred wherein the isocyanate
component is first partially or fully reacted with the hydrocarbon
intermediate or polyol to form an isocyanate-terminated prepolymer. The
same can be achieved by melt-polymerization. The partially or fully formed
prepolymer can then be subsequently reacted with the chain extender.
The polymerization of the reactants forming the thermoplastic
compatibilizer of the present invention can generally be carried out by
melt-polymerization in a substantially solvent-free and preferably
completely solvent-free environment. The hydrocarbon intermediate is
heated to a temperature of from about 80.degree. C. to about 160.degree.
C. The diisocyanate, such as MDI, is added and prepolymer formation
commences. After a short period of time, for example a couple or several
minutes whereby partial or total prepolymers have been formed, the chain
extender is added and the reaction carried out to completion. This method
allows ready reaction of the insoluble chain extender such as neopentyl
glycol with the diisocyanate inasmuch as neopentyl glycol does not
dissolve in the substantially hydrocarbon intermediate.
The formation of the compatibilizer is generally carried out in the
presence of small amounts of catalysts such as organo tin catalysts, e.g.,
stannous octoate, a preferred catalyst; stannous oleate; dibutyl tin
dioctoate; dibutyl tin dilaurate; and the like. Other organic catalysts
include iron acetylacetonate, magnesium acetylacetonate, and the like.
Tertiary organic amine catalysts, such as triethylamine, triethylene
diamine, and the like, can also be utilized. The amount of catalyst is
generally very small, from about 25 to about 1,000 parts per million and
desirably from about 40 to about 500 PPM by weight based upon the total
weight of the reactants.
Although various additives and fillers can be utilized as known to the art
and to the literature, such as pigments, lubricants, stabilizers,
antioxidants, anti-static agents, fire retardants, etc., the same are
generally not utilized in the preparation of the compatibilizer.
The thermoplastic polyurethane compatibilizer of the present invention has
soft segments as well as hard segments. The soft segments are generally
defined as being solely the hydrocarbon portion of the intermediate. This
is generally the entire portion of the hydrocarbon intermediate including
the functional (e.g. hydroxyl) end groups. The hard segments are defined
as everything else, e.g., the reaction of the intermediate terminal group
with the diisocyanate and the reaction of the chain extender with the
diisocyanate. The compatibilizers of the present invention desirably have
high amounts of soft segments such as at least about 25 or 35 percent by
weight, desirably from about 45 to about 90 percent by weight, and
preferably from about 60 to about 80 percent by weight based upon the
total weight of the thermoplastic polyurethane compatibilizer excluding
any additives, fillers, etc.
The physical blends of the thermoplastic elastomers and polyolefins of the
present invention are compatibilized by using small amounts of the
above-noted compatibilizing agent. Desirably thermoplastic elastomers
include thermoplastic polyester elastomers, thermoplastic polyamide
elastomers often referred to as polyether block amide thermoplastic
elastomers, and thermoplastic urethane elastomers, hereinafter referred to
as a thermoplastic urethane polymer. The thermoplastic urethane polymer
utilized can generally be any conventional type known to the art or
literature. Generally such urethane polymers are formed or derived from
polyester or polyether intermediates. The polyester intermediates can be
linear or branched and are produced by the esterification reaction of one
or more glycols with one or more dicarboxylic acids or anhydrides, or by
transesterification, i.e., the reaction of one or more glycols with esters
of dicarboxylic acids. Mole ratios in generally an excess of one mole of
glycol to acid are preferred so as to obtain intermediates having a
preponderance of terminal hydroxyl groups. The dicarboxylic acids can be
aliphatic, cycloaliphatic, aromatic, or combinations thereof having a
total of from 4 to about 15 to 20 carbon atoms and include succinic,
glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanoic,
isophthalic, terephthalic, cyclohexane dicarboxylic, and the like.
Anhydrides of the above dicarboxylic acids, such as phthalic anhydride,
tetrahydrophthalic anhydride, or the like and mixtures thereof can also be
utilized. The ester forming glycols can be aliphatic, aromatic, or
combinations thereof, have a total of from 2 to 12 carbon atoms. Examples
include: ethylene glycol, propylene-1,2-glycol, 1,3-propanediol,
butylene-1,3-glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
2,2-dimethylpropane-1,3-diol, 1,4-cyclohexanedimethanol, decamethylene
glycol, dodecamethylene glycol, hydroquinone bis(2-hydroxyethyl)ether;
2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and mixtures thereof.
Any suitable diisocyanate can be utilized as well as any conventional chain
extender with the above-noted polyester intermediate to form the
thermoplastic urethane polymer which is blended with the polyolefin.
Suitable diisocyanates include the above-noted diisocyanates set forth
with regard to the compatibilizing agent and include MDI, toluene
diisocyanate, isophorone diisocyanate, and the like, with MDI being
preferred. The chain extenders are generally diols having a molecular
weight of 500 less and thus include the chain extenders set forth
hereinabove with regard to the formation of the compatibilizing agent.
Desirable chain extenders include 1,4-butane diol, and the like.
The preparation of the above-known thermoplastic polyesterurethane polymers
are well known to the art and to the literature. Generally, a polyester
intermediate with one or more chain extenders are blended at a temperature
of from about 50 to about 100.degree. C. and then heated to a temperature
of about 100 to about 170.degree. C. Diisocyanate or a mixture thereof is
heated to approximately the same temperature and then mixed with the
blend. Since the reaction is exothermic, the temperature will increase
from about 200.degree. C. to about 270.degree. C. During the
polymerization of the thermoplastic urethane polymer, various polyurethane
catalysts can be utilized such as those noted hereinabove with regard to
the formation of the compatibilizing agent, and the same is hereby fully
incorporated by reference. Examples of suitable urethanes derived from
polyester intermediates are the various Estane.RTM. thermoplastic
polyurethanes manufactured by The BFGoodrich Company.
The hydroxyl terminated polyether intermediates can be polyether polyols
derived from a diol or polyol having a total of from 2 to 15 carbon atoms,
preferably an alkyl diol or glycol which is reacted with an ether
comprising an alkylene oxide having from 2 to 6 carbon atoms, typically
ethylene oxide or propylene oxide, or mixtures thereof. For example,
hydroxyl functional polyether can be produced by first reacting propylene
glycol with propylene oxide followed by subsequent reaction with ethylene
oxide. Primary hydroxyl groups resulting from ethylene oxide are more
reactive than secondary hydroxyl groups and thus are preferred. Useful
commercial polyether polyols include poly(ethylene glycol), poly(propylene
glycol), poly-(propylene-ethylene glycol), poly (tetramethylene ether
glycol) (PTMEG), copolyether produced from tetrahydrofuran (THF) and
ethylene oxide or THF and propylene oxide, glycerol adduct comprising
trimethylolpropane reacted with propylene oxide, pentaerythritol adduct
comprising pentaerythritol reacted with propylene oxide, and similar
hydroxyl functional polyethers or mixtures thereof. Polyether polyols
further include polyamide adducts of an alkylene oxide and can include,
for example, ethylenediamine adduct comprising the reaction product of
ethylenediamine and propylene oxide, diethylenetriamine adduct comprising
the reaction product of ethylenediamine and propylene oxide, and similar
polyamide type polyether polyols.
The above-noted polyether intermediates are reacted with conventional and
known diisocyanates as well as chain extenders such as those set forth
hereinabove with regard to the formation of a thermoplastic urethane
polymer derived from a polyester intermediate and thus the same is fully
incorporated by reference. Rather than to repeat the types of
diisocyanates and chain extenders, it is merely noted that MDI is the
preferred diisocyanate and that 1,4-butane diol is the preferred chain
extender. The preparation of the thermoplastic urethane polymer derived
from a polyether intermediate is the same as set forth with regard to
those derived from a polyester intermediate set forth hereinabove and the
same is hereby fully incorporated by reference. Examples of urethane
polymers derived from an ether intermediate include the various
Estane.RTM. thermoplastic polyurethanes and the various Stat-Rite.TM.
static dissipative polymers manufactured by The BFGoodrich Company.
The thermoplastic polyester elastomers are multi-block copolymers which can
be represented by generalized formula (--A--B--).sub.n. Polyester
elastomers contain repeating high melting blocks which are capable of
crystallization (hard segments) and amorphous blocks having a relatively
low glass transition temperature (soft segments). Typically the hard
segments are composed of multiple short chain ester units such as
tetramethylene terephthalate units and the soft segments are derived from
aliphatic polyether or polyester glycols having from 2 to about 20 carbon
atoms. At useful service temperatures, the polyester elastomers resist
deformation because of the presence of a network of microcrystallites
formed by partial crystallization of hard segments. The microcrystallites
function as physical crosslinks. At processing temperatures, the
crystallites melt to yield a polymer melt which after shaping by molding,
for example, retains its form upon cooling due to re-crystallization of
the hard segments. As in the case of the polyurethanes, a variety of
starting materials can be used for the preparation of polyester
elastomers. By varying the ratio of hard to soft segments polyesters
ranging from soft elastomers to relatively hard elastoplastics can be
obtained.
Copolyesters derived from terephthalic acid, tetramethylene glycol, and
poly(tetramethyleneoxide) glycol are desired. Such compositions contain
from about 30 percent to about 95 percent by weight of tetramethylene
terephthalate units. Moreover, polymers in which a portion of the
tetramethylene terephthalate units are replaced by tetramethylene
isophthalate or tetramethylene phthalate were also desired. Such
thermoplastic polyester elastomers exhibit good tear strength, elasticity,
low temperature flexibility and strength at elevated temperatures. They
also crystallize rapidly. These thermoplastic polyester elastomers are
commercially available as Hytrel.RTM. polyester elastomers from DuPont.
Such polyester elastomers are more fully described in U.S. Pat. Nos.
3,651,014; 3,763,109; and 3,755,146, which are hereby fully incorporated
by reference.
The copolyesters are readily prepared by melt polymerization. An agitated
mixture of dimethyl terephthalate, poly(tetramethylene oxide) glycol and
excess tetramethylene glycol is heated in the presence of a titanate
catalyst. Methanol resulting from ester exchange is removed by fractional
distillation after which the temperature is raised to about 250.degree. C.
while the pressure is reduced to less than 133 Pa. Measurement of the
viscosity of the reaction mass permits the course of the polymerization to
be followed. Temperatures above 260.degree. C. lead to excessive rates of
degradation.
These and other thermoplastic polyester elastomers which are known to the
literature and to the art can be utilized in the present invention. For
example, the polyester elastomers can be utilized as set forth in
"Thermoplastic Elastomers" by Legge, Holden, and Schroeder, Hanser
publishers, New York, N.Y., 1987, which is hereby fully incorporated by
reference.
The thermoplastic polyamide elastomers, e.g., polyether block amide
thermoplastic elastomers can be synthesized by many different methods
using different linkages between the polyether and polyamide blocks. For
example, amide linkages can be obtained by the reaction of dicarboxylic
polyether blocks with diamine polyether blocks or diamine polyamide blocks
with dicarboxylic polyether blocks in the molten state, see French Patent
No. 1,603,901; Japanese patent 19,846R; U.S. Pat. No. 3,454,534; and
United Kingdom patent 1,108,812, which are hereby fully incorporated by
reference. Urethane linkages can be obtained by the reaction of poly
(oxyethylene) .alpha..omega.-bischloroformate with adipoyl chloride and
piperazine in solution, see United Kingdom patent 1,098,475, hereby fully
incorporated by reference. The reaction of poly(oxethylene) diisocyanate
with a diamine aromatic polyamide to produce polyamide polyether block
copolymers with urea linkages, see Japanese patent 24,285Q, hereby fully
incorporated by reference. Polyether-amide block copolymers having an
ester linkage can be obtained by the melt polymerization of a dicarboxylic
polyamide and a polyether diol. For example, the reaction of a
dicarboxylic acid polyamide based on caprolactam and poly(oxyethylene)
dihydroxy at 250.degree. C. with paratoluene sulfonic acid as a catalyst,
see United Kingdom patent 1,110,394, hereby fully incorporated by
reference. Another route is the reaction of a 36 carbon atom fatty acid
dimer and a diamine with a polyoxyethylene dihydroxy without catalyst at
250.degree. C., see French patent 2,178,205, which is hereby fully
incorporated by reference.
Generally, the polyether block amide thermoplastic elastomer is obtained by
the molten state polycondensation reaction of polyether diol blocks and
dicarboxylic polyamide blocks. The dicarboxylic polyamide blocks are
produced by the reaction of polyamide precursors with a dicarboxylic acid
chain limiter. The reaction is achieved at high temperature (higher than
230.degree. C.) and generally under pressure (up to 25 bars). The
molecular weight of the polyamide block is controlled by the amount of
chain limiter. The polyamide precursors can be selected from the
following:
amino acids (aminoundecanoic acid, aminododecanoic acid)
lactams (caprolactam, Lauryllactam)
dicarboxylic acids (adipic acid, azelaic acid, dodecanedioic acid)
diamines (hexamethylene diamine, dodecamethylene diamine).
Dihydroxy polyether blocks are produced by two different reactions:
anionic polymerization of ethylene oxide and propylene oxide for
polyoxyethylene dihydroxy and polyoxypropylene dihydroxy
cationic polymerization of tetrahydrofuran for polyoxytetramethylene
dihydroxy
The block copolymerization is a polyesterification achieved at high
temperature (230-280.degree. C.) under vacuum (0.1 to 10 Torrs) and
requires the use of an appropriate catalyst. The preparation of such
thermoplastic polyether block amide thermoplastic elastomers is well known
to the art and to the literature.
The weight average molecular weight of the various thermoplastic elastomers
which are blended with the polyolefins is generally from about 20,000 to
about 500,000 and preferably from about 80,000 to about 300,000 as
determined by gel permeation chromatography. The weight average molecular
weight of the polyester or polyether intermediates with regard to the
formation of the thermoplastic urethane polymer is generally from about
250 to about 5,000 and preferably from about 1,000 to about 4,000.
The polyolefins utilized in the blend are made from monomers having from 2
to 4 carbon atoms with examples including polyethylene (including high
density polyethylene, low density polyethylene, linear low density
polyethylene and the like), polybutylene and their copolymers, with
polypropylene including atactic and syndiotactic polypropylene, as well as
blends of polypropylene with elastomers, commonly referred to as TPO
(thermoplastic polyolefins) being preferred. The weight average molecular
weight of such polyolefins is generally from about 40,000 to about
2,000,000, and preferably from about 100,000 to about 1,500,000.
The amount of the thermoplastic elastomers utilized in forming the physical
blend is generally from about 5 percent to about 95 percent by weight, and
preferably from about 15 to about 60 percent by weight based upon the
total weight of the thermoplastic elastomer and the polyolefin. The amount
of the polyolefin utilized in the blend is a complementary amount.
The amount of the compatibilizing agent of the present invention utilized
to form the compatibilized blend is unexpectedly a very low level.
Naturally, the optimum amount will vary depending upon the type of
thermoplastic elastomers, the type of particular polyolefin, and the like.
Generally, the amount of compatibilizing agent is from about 0.25 to about
15 parts by weight and desirably from about 0.5 or 0.75 to about 6 or 10
parts by weight for every 100 parts by weight of the thermoplastic
elastomer and the polyolefin blend.
The polyolefin and the thermoplastic elastomer are mixed or blended in a
suitable manner along with the compatibilizing agent to achieve a
compatibilized blend. The mixing can utilize conventional melt processing
techniques and can either be batch or continuous such as through the use
of a single or a twin screw extruder. The mixing temperature is generally
above the melting point of the polyolefin, the thermoplastic elastomer and
the compatibilizing agent. Such temperatures are generally from about
180.degree. C. to about 240.degree. C. The mixing time will naturally vary
depending upon the amount of components blended together.
When compatibilized, the thermoplastic polyolefin blends have been found to
have improved properties such as impact resistance, good tensile strength,
low delamination, good tear resistance, low abrasion, and the like over
noncompatibilized blends of the same two polymers as fully shown in the
various examples.
The compatibilized blends of the present invention can be used wherever
blends having the above-noted properties are desired, as in automotive
components, for example rocker panels, body side moldings, quarter panels,
and the like; in electronic component packaging items; in business
machines such as housing and the like; and for auxiliary devices for the
electronic industry.
The invention will be better understood by reference to the following
examples which serve to illustrate but not limit the present invention.
SYNTHESES OF COMPATIBILIZERS
Polyurethanes were prepared by either the random melt polymerization method
or the prepolymer method. In the random melt polymerization method, the
polyol and chain extender are blended together at 100-150.degree. C.
Diphenylmethanediisocyanate (MDI) is heated separately to 100-150.degree.
C., then mixed with the blend. The reactants are vigorously mixed for 3-4
minutes. The polymer melt is discharged into a cooled, teflon-coated pan,
cured at 70.degree. C. for 1 week, then granulated. In the prepolymer
method, the polyol is heated to 100-150.degree. C. MDI is separately
heated to 100-150.degree. C., then mixed with the polyol and allowed to
react for 1-2 minutes. The chain extender is added, and the reaction
continues for an additional 1.5-3 minutes. The polymer melt is then
treated as described above. The melt index values were obtained by
ASTM-D-1238.
EXAMPLE 1
Pripol 2033 (150.0 g, MW 570) was heated to 100.degree. C. with stirring.
MDI (65.2 g), preheated to 100.degree. C., was added. The mixture was
allowed to react for 3 minutes.
EXAMPLE 2
Kraton Liquid.TM. HPVM-2203 (100.0 g, MW 3577), Pripol 2033 (100.0 g, MW
570), and stannous octoate (0.012 g) were heated to 100.degree. C. with
stirring. MDI (51.0 g), preheated to 100.degree. C., was added. The
mixture was allowed to react for 3 minutes.
EXAMPLE 3
Kraton Liquid.TM. HPVM-2203 (180.0 g, MW 3577) and stannous octoate (0.012
g) were heated to 120.degree. C. with stirring. MDI (55.0 g), preheated to
120.degree. C., was added. After 1.5 minutes of reaction, 20.0 g of
neopentyl glycol (NPG) was added. The mixture was allowed to react for an
additional 1.5 minutes. This polymerization was repeated. The granulated
polymers were blended to give a polyurethane with melt index of 44
(190.degree. C., 8700 g).
EXAMPLE 4
Kraton Liquid.TM. L-2203 (180.5 g, MW 3250) and stannous octoate (0.012)
were heated to 120.degree. C. with stirring. MDI (54.7 g), preheated to
120.degree. C., was added. After 2 minutes of reaction, NPG (19.5 g) was
added. The mixture was allowed to react for an additional 2 minutes. This
polymerization was repeated nine times. The granulated polymers were
blended to give a polyurethane with melt index of 6 (190.degree. C., 8700
g).
EXAMPLE 5
Priplast 3197 (183.3 g, MW 2110), NPG (16.7 g), and stannous octoate (0.012
g) were heated to 120.degree. C. with stirring. MDI (62.5 g), preheated to
120.degree. C., was added. The mixture was allowed to react for 4 minutes.
This polymerization was repeated. The granulated polymers were blended to
give a polyurethane with melt index of 15 (190.degree. C., 8700 g).
EXAMPLE 6
Kraton Liquid.TM. L-2203 (183.2 g, 3250 MW) and stannous octoate (0.012)
were heated to 150.degree. C. with stirring. MDI (60.2 g), preheated to
150.degree. C., was added. After 2 minutes of reaction, 16.8 g of
1,4-butanediol (BDO) was added. The mixture was allowed to react for an
additional 2 minutes, giving a polyurethane with melt index of
4(210.degree. C., 3800 g).
EXAMPLE 7
Kraton Liquid.TM. L-2203 (177.8 g, 3250 MW) and stannous octoate (0.012 g)
were heated to 150.degree. C. with stirring. MDI (60.1 g), preheated to
150.degree. C., was added. After 2 minutes of reaction, 1,6-hexanediol
(22.2 g) was added. The mixture was allowed to react for an additional 2
minutes, giving a polyurethane with melt index of 3 (210.degree. C., 3800
g).
EXAMPLE 8
Kraton Liquid.TM. L-2203 (172.7 g, 3250 MW) and stannous octoate (0.012 g)
were heated to 150.degree. C. with stirring. MDI (60.1 g), preheated to
150.degree. C., was added. After 2 minutes of reaction,
1,4-cyclohexanedimethanol (27.3 g) was added. The mixture was allowed to
react for an additional 2 minutes, giving a polyurethane with melt index
of 14 (210.degree. C., 3800 g).
EXAMPLE 9
Kraton Liquid.TM. L-2203 (180.5 g, 3250 MW) and stannous octoate (0.012 g)
were heated to 150.degree. C. with stirring. MDI (60.1 g) preheated to
150.degree. C., was added. After 2 minutes of reaction, 1,5-pentanediol
(19.5 g) was added. The mixture was allowed to react for an additional 2
minutes, giving a polyurethane with melt index of 16 (210.degree. C., 3800
g).
EXAMPLE 10
Kraton Liquid.TM. L-2203 (161.8 g, 3250 MW) and dibutyltin dilaurate (0.012
g) were heated to 150.degree. C. with stirring. MDI (58.4 g), preheated to
150.degree. C., was added. After 1 minute of reaction, hydroquinone
bis(2-hydroxyethyl)ether (38.2 g) was added. The mixture was allowed to
react for an additional 3 minutes, giving a polyurethane with melt index
of 17 (210.degree. C., 3800 g).
EXAMPLE 11
Krasol LBH (180.1 g 3522 MW) and stannous octoate (0.012) were heated to
150.degree. C. with stirring. MDI (60.8 g), preheated to 150.degree. C.,
was added. After 2 minutes of reaction, NPG (19.9 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 31 (175.degree. C., 5000 g).
EXAMPLE 12
Polytail HA (183.4 g, 2197 MW) and stannous octoate (0.012 g) were heated
to 150.degree. C. with stirring. MDI (57.2 g), preheated to 150.degree.
C., was added. After 2 minutes of reaction, NPG (16.6 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 31 (175.degree. C., 5000 g).
EXAMPLE 13
Liquiflex H (181.5 g, 2800 MW) and stannous octoate (0.012 g) were heated
to 150.degree. C. with stirring. MDI (50.2 g), preheated to 150.degree.
C., was added. After 2 minutes of reaction, NPG (18.5 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 37 (175.degree. C., 5000 g).
EXAMPLE 14
Polytail H (134.8 g, 2252 MW) and stannous octoate (0.012) were heated to
120.degree. C. with stirring. MDI (36.5 g), preheated to 120.degree. C.,
was added. After 2 minutes of reaction, NPG (15.2 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 86 (210.degree. C., 3800 g).
EXAMPLE 15
Polytail HA (183.4 g, 2197 MW) and stannous octoate (0.012 g) were heated
to 150.degree. C. with stirring. MDI (58.2 g), preheated to 150.degree.
C., was added. After 2 minutes of reaction, NPG (16.6 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 32 (190.degree. C., 8700 g).
EXAMPLE 16
Krasol LBH (180.1 g, 3522 MW) and stannous octoate (0.012 g) were heated to
150.degree. C. with stirring. MDI (61.9 g), preheated to 150.degree. C.,
was added. After 2 minutes of reaction, NPG (19.9 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 25 (190.degree. C., 8700 g).
EXAMPLE 17
Kraton Liquid.TM. L-2203 (169.5 g, 3250 MW),
2-butyl-2-ethyl-1,3-propanediol (BEPD, 30.5 g), and stannous octoate
(0.012 g) were heated to 150.degree. C. with stirring. MDI (59.5 g),
preheated to 150.degree. C., was added. The mixture was allowed to react
for 4 minutes, giving a polyurethane with melt index of 112 (210.degree.
C., 3800 g).
EXAMPLE 18
Kraton Liquid.TM. L-2203 (180.5 g, 3250 MW), and stannous octoate (0.012 g)
were heated to 120.degree. C. with stirring. MDI (54.6 g), preheated to
120.degree. C., was added. After 2 minutes of reaction, NPG (19.5) was
added. The mixture was allowed to react for an additional 2 minutes,
giving a polyurethane with melt index of 16 (190.degree. C., 8700 g).
EXAMPLE 19
Kraton Liquid.TM. L-2203 (169.5 g, 3250 MW), BEPD (30.5 g), and stannous
octoate (0.012 g) were heated to 150.degree. C. with stirring. MDI (59.6
g), preheated to 150.degree. C., was added. The mixture was allowed to
react for 4 minutes, giving a polyurethane with melt index of 13
(190.degree. C., 8700 g).
EXAMPLE 20
Kraton Liquid.TM. L-2203 (104.3 g, 3250 MW), Pripol 2033 (95.7 g, 570 MW),
and stannous octoate (0.012 g) were heated to 120.degree. C. with
stirring. MDI (50.0 g), preheated to 120.degree. C., was added. The
mixture was allowed to react for 4 minutes, giving a polyurethane with
melt index of 144 (190.degree. C., 8700 g).
EXAMPLE 21
Priplast 3197 (166.4 g, 2110 MW), and stannous octoate (0.012 g) were
heated to 120.degree. C. with stirring. MDI (58.3 g), preheated to
120.degree. C., was added. After 2 minutes of reaction, BDO (13.6 g) was
added. The mixture was allowed to react for an additional 2 minutes,
giving a polyurethane with melt index of <1 (190.degree. C., 2160 g).
EXAMPLE 22
Priplast 3197 (165.0 g, 2110 MW), and stannous octoate (0.012 g) were
heated to 120.degree. C. with stirring. MDI (56.3 g), preheated to
120.degree. C., was added. After 2 minutes of reaction, NPG (15.0) was
added. The mixture was allowed to react for an additional 2 minutes,
giving a polyurethane with melt index of 1 (190.degree. C., 2160 g).
EXAMPLE 23
Priplast 3197 (160.6 g, 2110 MW) and stannous octoate (0.012 g) were heated
to 120.degree. C. with stirring. MDI (49.9 g), preheated to 120.degree.
C., was added. After 2 minutes of reaction, BEPD (19.4 g) was added. The
mixture was allowed to react for an additional 2 minutes, giving a
polyurethane with melt index of 30 (190.degree. C., 2160 g).
EXAMPLE 24
Kraton Liquid.TM. L-2203 (173.6 g, 3250 MW) and stannous octoate (0.012 g)
were heated to 120.degree. C. with stirring. MDI (72.3 g), preheated to
120.degree. C., was added. After 2 minutes of reaction, NPG (26.4 g) was
added. The mixture was allowed to react for an additional 2 minutes. This
polymerization was repeated four times. The granulated polymers were
blended to give a polyurethane with melt index of 7 (190.degree. C., 8700
g).
COMPARATIVE EXAMPLE 1
Polytetramethyleneadipate glycol (145.9 g, 2047 MW), Kraton Liquid.TM.
L-2203 (19.8 g, 3250 MW), and BDO (15.2 g) were heated to 120.degree. C.
with stirring. MDI (60.4 g), preheated to 120.degree. C., was added. The
reaction was allowed to react for 3 minutes. The polymerization was
repeated. The granulated polymers were blended to give a polyurethane with
melt index of 19 (210.degree. C., 3800 g).
POLYMER COMPOUNDING
Compound example numbers 25-51 and 58-66 were prepared using a Werner
Pfleiderer ZSK-30 twin screw compounding extruder equipped with a strand
die. In this method, a physical mixture of the components were fed into
the extruder using a loss-in-weight feeder. The melt temperatures were
generally 210-220.degree. C. The extruded strands were chopped into
uniform pellets. The pellets were processed by injection molding and/or
film extrusion for property measurements. Compound example numbers 52-57
were prepared in a Brabender Prep Mixer. In this method, the components
were charged into the mixer and mixed for 3 minutes after an initial
static heating period of 5 minutes. The melt temperatures were generally
190-200.degree. C. The blends obtained in this method were compression
molded into sheets for property measurements.
TABLE I
__________________________________________________________________________
Ex 25
Ex 26
Ex 27
Ex 28
Ex 29
Ex 30
Ex 31
Ex 32
Ex 33
Ex 34
Ex 35
Ex 36
__________________________________________________________________________
Polyester TPU (1)
60 57 57 57 57 -- -- 57 57 57 57 57
Polyester TPU (2) -- -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (3) -- -- -- -- -- 60 57 -- -- -- -- --
Polyether TPU (4) -- -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (5) -- -- -- -- -- -- -- -- -- -- --
Profax 6523 (6) 40 38 38 38 38 40 38 38 38 38 38 38
Rexene 41E2 (7) -- -- -- -- -- -- -- -- -- -- -- --
Exxelor PO-1015 (8) -- -- -- -- -- -- -- -- -- -- -- --
Bayon YM312 (9) -- -- -- -- -- -- -- -- -- -- -- --
Hytrel 5544 (10) -- -- -- -- -- -- -- -- -- -- -- --
Pebax MV 1074(11) -- -- -- -- -- -- -- -- -- -- -- --
Example 1 -- -- 5 -- -- -- -- -- -- -- -- --
Example 2 -- -- -- 5 -- -- -- -- -- -- -- --
Example 3 -- -- -- -- 5 -- -- -- -- -- -- --
Example 4 -- -- -- -- -- -- 5 -- -- -- -- --
Example 5 -- -- -- -- -- -- -- 5 -- -- -- --
Example 6 -- -- -- -- -- -- -- -- 5 -- -- --
Example 7 -- -- -- -- -- -- -- -- -- 5 -- --
Example 8 -- -- -- -- -- -- -- -- -- -- 5 --
Example 9 -- -- -- -- -- -- -- -- -- -- -- 5
Example 10 -- -- -- -- -- -- -- -- -- -- -- --
Example 11 -- -- -- -- -- -- -- -- -- -- -- --
Example 12 -- -- -- -- -- -- -- -- -- -- -- --
Example 13 -- -- -- -- -- -- -- -- -- -- -- --
Example 14 -- -- -- -- -- -- -- -- -- -- --
Example 15 -- -- -- -- -- -- -- -- -- -- -- --
Example 16 -- -- -- -- -- -- -- -- -- -- -- --
Example 17 -- -- -- -- -- -- -- -- -- -- -- --
Example 18 -- -- -- -- -- -- -- -- -- -- -- --
Example 19 -- -- -- -- -- -- -- -- -- -- -- --
Example 20 -- -- -- -- -- -- -- -- -- -- -- --
Example 21 -- -- -- -- -- -- -- -- -- -- -- --
Example 22 -- -- -- -- -- -- -- -- -- -- -- --
Example 23 -- -- -- -- -- -- -- -- -- -- -- --
Ex 24 -- -- -- -- -- -- -- -- -- -- -- --
Comp Ex 1 -- -- -- -- -- -- -- -- -- -- -- --
Kraton Liquid L-2203 -- -- -- -- -- -- -- -- -- -- -- --
Properties
Izod, ft-lbs/inch 5.4 8 9.1 13.5 22 2.3 8.5 19.6 20.3 20.2 17.8 16.9
Flexural Modulus, psi --
95 K 77 K 65 K 61 K 53 K 45
K 64 K 62 K 67 K 65 K 64 K
Tensile Strength, psi --
-- -- -- -- -- -- --
-- -- -- --
Elongation, % -- -- -- -- -- -- -- 254 251 269 271 263
Tear Resistance, ft-lbs/inch. -- -- -- -- -- -- -- -- -- -- -- --
Taber Abrasion, g loss --
-- -- -- -- -- -- -- -- --
-- --
Static decay +5,000 volts, -- -- -- -- . -- -- -- -- -- -- -- --
sec.
Static decay -5,000 volts, -- -- -- -- -- -- -- -- -- -- -- --
sec.
Surface Resistivity, ohms -- -- -- -- -- -- -- -- -- -- -- --
Surface (12) -- del del sl del v sl del del -- sl del sl del sl del sl
del
del
__________________________________________________________________________
(1) Poly(tetramethylene adipate) glycol with 59% hard segment.
(2) Poly(tetramethyleneadipate) glycol with 45% hard segment.
(3) Poly(tetramethylene ether) glycol with 62% hard segment.
(4) Poly(tetramethylene ether) glycol with 43% hard segment.
(5) Poly(oxyethylene)glycol with 36% hard segment.
(6) Polypropylene homopolymer.
(7) Polypropylene homopolymer.
(8) Maleic anhydride functionalized polypropylene.
(9) PEGgrafted acrylic copolymer.
(10) Copolyester
(11) Copolyamide
(12) Surfaces of molded plaques were judged for delamination (del); v
(very), sl (slight), sev (severe).
The above properties were obtained by the following ASTM test methods.
Property Test Method
Izod Impact ASTM D-256
Flexural Modulus ASTM D-790
Tensile strength/elongation ASTM D-412
Tear Resistance ASTM D-624
Taber Abrasion ASTM D-3389
Surface Resistivity ASTM D-257
Static decay FTMS 101C, Method 4046.1
TABLE II
__________________________________________________________________________
Ex 37
Ex 38
Ex 39
Ex 40
Ex 41
Ex 42
Ex 43
Ex 44
Ex 45
Ex 46
Ex 47
Ex 48
__________________________________________________________________________
Polyester TPU (1)
57 57 57 57 57 57 57 57 57 -- -- --
Polyester TPU (2) -- -- -- -- -- -- -- -- -- 60 57 57
Polyether TPU (3) -- -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (4) -- -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (5) 38 38 38 38 38 38 38 38 38 -- -- --
Profax 6523 (6) -- -- -- -- -- -- -- -- -- -- -- --
Rexene 41E2 (7) -- -- -- -- -- -- -- -- -- 40 38 38
Exxelor PO-1015 (8) -- -- -- -- -- -- -- -- -- -- -- --
Bayon YM312 (9) -- -- -- -- -- -- -- -- -- -- -- --
Hytrel 5544 (10) -- -- -- -- -- -- -- -- -- -- -- --
Pebax MV 1074 (11) -- -- -- -- -- -- -- -- -- -- -- --
Example 1 -- -- -- -- -- -- -- -- -- -- -- --
Example 2 -- -- -- -- -- -- -- -- -- -- -- --
Example 3 -- -- -- -- -- -- -- -- -- -- -- --
Example 4 -- -- -- -- -- -- -- -- -- -- -- 5
Example 5 -- -- -- -- -- -- -- -- -- -- -- --
Example 6 -- -- -- -- -- -- -- -- -- -- -- --
Example 7 -- -- -- -- -- -- -- -- -- -- -- --
Example 8 -- -- -- -- -- -- -- -- -- -- -- --
Example 9 -- -- -- -- -- -- -- -- -- -- -- --
Example 10 5 -- -- -- -- -- -- -- -- -- -- --
Example 11 -- 5 -- -- -- -- -- -- -- -- -- --
Example 12 -- -- 5 -- -- -- -- -- -- -- -- --
Example 13 -- -- -- 5 -- -- -- -- -- -- -- --
Example 14 -- -- -- -- 5 -- -- -- -- -- -- --
Example 15 -- -- -- -- -- 5 -- -- -- -- -- --
Example 16 -- -- -- -- -- -- 5 -- -- -- -- --
Example 17 -- -- -- -- -- -- -- 5 -- -- -- --
Example 18 -- -- -- -- -- -- -- -- -- -- -- --
Example 19 -- -- -- -- -- -- -- -- -- -- -- --
Example 20 -- -- -- -- -- -- -- -- -- -- -- --
Example 21 -- -- -- -- -- -- -- -- -- -- -- --
Example 22 -- -- -- -- -- -- -- -- -- -- -- --
Example 23 -- -- -- -- -- -- -- -- -- -- -- --
Example 24 -- -- -- -- -- -- -- -- 5 -- 5 --
Comp Ex 1 -- -- -- -- -- -- -- -- -- -- -- --
Kraton Liquid L-2203 -- -- -- -- -- -- -- -- -- -- -- --
Properties
Izod, ft-lbs/inch 19.8 10.2 14.1 11 10.6 10 9.2 17.1 17.9 -- -- --
Flexural Modulus, psi 61 K
67 K 70 K 61 K 92 K 63 K 83
K 73 K 67 K -- -- --
Tensile Strength, psi --
-- -- -- 4090 4720 4920
4790 -- 4472 4829 6012
Elongation, % 263 266 263
264 258 270 277 266 249 404
439 501
Tear Resistancc, ft-lbs/inch -- -- -- -- -- -- -- -- -- 597 545 717
Tabcr Abrasion, g Ioss --
-- -- -- -- -- -- -- --
0.61 0.26 0.14
Static decay +5,000 volts, -- -- -- -- -- -- -- -- -- -- -- --
sec.
Static dccay -5,000 volts, -- -- -- -- -- -- -- -- -- -- -- --
sec.
Surface Resistivity, ohms -- -- -- -- -- -- -- -- -- -- -- --
Surface (12) v sl v sl v sl v sl -- -- -- -- sev -- -- --
del del del del del
__________________________________________________________________________
(1) Poly(tetramethylene adipate) glycol with 59% hard segment.
(2) Poly(tetramethylene adipate) glycol with 45% hard segment.
(3) Poly(tetramethylene ether) glycol with 62% hard segment.
(4) Poly(tetramethylene ether) glycol with 43% hard segment.
(5) Poly(oxyethylene) glycol with 36% hard segment.
(6) Polypropylene homopolymer.
(7) Polypropylene homopolymer.
(8) Maleic anhydride functionalized polypropylene.
(9) PEGgrafted acrylic copolymer.
(10) Copolyester
(11) Copolyamide
(12) Surfaces of molded plaques were judged for delamination (del); v
(very), sl (slight), sev (severe).
TABLE III
__________________________________________________________________________
Ex 49
Ex 50
Ex 51
Ex 52
Ex 53
Ex 54
Ex 55
Ex 56
Ex 57
Ex 58
Ex 59
Ex 60
__________________________________________________________________________
Polyester TPU (1)
-- -- -- -- -- -- -- -- -- -- -- --
Polyester TPU (2) -- -- -- 60 57 57 -- -- -- -- -- --
Polyester TPU (3) -- -- -- -- -- -- -- -- -- -- -- --
Polyester TPU (4) 60 57 57 -- -- -- 60 57 57 -- -- --
Polyester TPU (5) -- -- -- -- -- -- -- -- -- -- 25 25
Profax 6523 (6) -- -- -- -- -- -- -- -- -- -- -- --
Rexene 41E2 (7) 40 38 38 40 38 38 40 38 38 100 75 69
Exxelor PO-1015 (8) -- -- -- -- -- -- -- -- -- -- -- --
Bayon YM312 (9) -- -- -- -- -- -- -- -- -- -- -- 5
Hytrel 5544 (10) -- -- -- -- -- -- -- -- -- -- -- --
Pebax MV 1074 (11) -- -- -- -- -- -- -- -- -- -- -- --
Example 1 -- -- -- -- -- -- -- -- -- -- -- --
Example 2 -- -- -- -- -- -- -- -- -- -- -- --
Example 3 -- -- -- -- -- -- -- -- -- -- -- --
Example 4 -- -- 5 -- 5 -- -- 5 -- -- -- --
Example 5 -- -- -- -- -- -- -- -- -- -- -- --
Example 6 -- -- -- -- -- -- -- -- -- -- -- --
Example 7 -- -- -- -- -- -- -- -- -- -- -- --
Example 8 -- -- -- -- -- -- -- -- -- -- -- --
Example 9 -- -- -- -- -- -- -- -- -- -- -- --
Example 10 -- -- -- -- -- -- -- -- -- -- -- --
Example 11 -- -- -- -- -- -- -- -- -- -- -- --
Example 12 -- -- -- -- -- -- -- -- -- -- -- --
Example 13 -- -- -- -- -- -- -- -- -- -- -- --
Example 14 -- -- -- -- -- -- -- -- -- -- -- --
Example 15 -- -- -- -- -- -- -- -- -- -- -- --
Example 16 -- -- -- -- -- -- -- -- -- -- -- --
Example 17 -- -- -- -- -- -- -- -- -- -- -- --
Example 18 -- -- -- -- -- -- -- -- -- -- -- --
Example 19 -- -- -- -- -- -- -- -- -- -- -- --
Example 20 -- -- -- -- -- -- -- -- -- -- -- --
Example 21 -- -- -- -- -- -- -- -- -- -- -- --
Example 22 -- -- -- -- -- -- -- -- -- -- -- --
Example 23 -- -- -- -- -- -- -- -- -- -- -- --
Example 24 -- 5 -- -- -- -- -- -- -- -- -- --
Comp Ex 1 -- -- -- -- -- -- -- -- -- -- -- --
Kraton Liquid L-2203 -- -- -- -- -- 5 -- -- 5 -- -- --
Properties
Izod, ft-lbs/inch -- -- -- -- -- -- -- -- -- 0.94 1.51 2.1
Flexural Modulus, psi -- -- -- -- -- -- -- -- -- -- -- --
Tensile Strength, psi 2855 2891 3733 1267 3121 1830 1528 1757 1097 5400
3150 3640
Elongation, % 471 508 525 29 289 13 14 147 7 16 11 81
Tear Resistance, ft-lbs/inch 436 338 549 731 821 366 545 742 428 -- --
927
Taber Abrasion, g loss 0.54 0.53 0.44 -- -- -- -- -- -- -- -- --
Static decay +5,000 --
-- -- -- -- -- -- -- --
-- 0.4 0.11
volts, sec
Static decay -5,000 -- -- -- -- -- -- -- -- -- -- 0.41 0.13
volts, sec
Surface Resistivity, -- -- -- -- -- -- -- -- -- 3.4E+12 3.0E+11 1.2E+11
ohms
Surface (12) -- -- -- -- -- -- -- -- -- -- -- --
__________________________________________________________________________
(1) Poly(tetramethylene adipate) glycol with 59% hard segment
(2) Poly(tetramethyleneadipate) glycol with 45% hard segment
(3) Poly(tetramethylene ether) glycol with 62% hard segment
(4) Poly(tetramethylene ether) glycol with 43% hard segment
(5) Poly(oxyethylene) glycol with 36% hard segment
(6) Polypropylene homopolymer
(7) Polypropylene homopolymer
(8) Maleic anhydride functionalized polypropylene
(9) PEGgrafted acrylic copolymer
(10) Copolyester
(11) Copolyamide
(12) Surfaces of molded plaques were judged for delamination (del); v
(very), sl (slight), sev (severe).
TABLE IV
__________________________________________________________________________
Ex 61
Ex 62
Ex 63
Ex 64
Ex 65
Ex 66
Ex 67
Ex 68
Ex 69
Ex 70
Ex 71
__________________________________________________________________________
Potyester TPU (1)
-- -- -- -- -- -- -- -- -- -- --
Polyester TPU (2) -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (3) -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (4) -- -- -- -- -- -- -- -- -- -- --
Polyether TPU (5) 25 25 25 25 25 25 -- -- -- -- --
Profax 6523 (6) -- -- -- -- -- -- -- -- -- -- --
Rexene 41E2 (7) 69 69 69 69 69 69 -- -- -- -- --
Exxelor PO-1015 (8) -- -- -- -- -- -- -- -- -- -- --
Bayon YM312 (9) 5 5 5 5 5 5 -- -- -- -- --
Hytret 5544 (10) -- -- -- -- -- -- -- 25 25 -- --
Pebax MV 1074 (11) -- -- -- -- -- -- -- -- -- 25 25
Example 1 -- -- -- -- -- -- -- -- -- -- --
Example 2 -- -- -- -- -- -- -- -- -- -- --
Example 3 -- -- -- -- -- -- -- -- -- -- --
Example 4 -- -- -- -- -- -- -- -- -- -- --
Example 5 -- -- -- -- -- -- -- -- -- -- --
Example 6 -- -- -- -- -- -- -- -- -- -- --
Example 7 -- -- -- -- -- -- -- -- -- -- --
Example 8 -- -- -- -- -- -- -- -- -- -- --
Example 9 -- -- -- -- -- -- -- -- -- -- --
Example 10 -- -- -- -- -- -- -- -- -- -- --
Example 11 -- -- -- -- -- -- -- -- -- -- --
Example 12 -- -- -- -- -- -- -- -- -- --
Example 13 -- -- -- -- -- -- -- -- -- -- --
Example 14 -- -- -- -- -- -- -- -- -- -- --
Example 15 -- -- -- -- -- -- -- -- -- -- --
Example 16 -- -- -- -- -- -- -- -- -- -- --
Example 17 -- -- -- -- -- -- -- -- -- -- --
Example 18 1 -- -- -- -- -- -- -- -- -- --
Example 19 -- 1 -- -- -- -- -- -- -- -- --
Example 20 -- -- 1 -- -- -- -- -- -- -- --
Example 21 -- -- -- 1 -- -- -- -- -- -- --
Example 22 -- -- -- -- 1 -- -- -- -- -- --
Example 23 -- -- -- -- -- 1 -- -- -- -- --
Example 24 -- -- -- -- -- -- 1 -- 1 -- --
Comp Ex 1 -- -- -- -- -- -- -- -- -- -- 1
Kraton Liquid L-2203 -- -- -- -- -- -- -- -- -- -- --
Properties -- -- -- -- -- -- -- -- -- -- --
Izod, ft-lbs/inch 12.3 12.9 7.7 6.28 7.09 6.45 -- -- -- -- --
Flexural Modulus, psi -- -- -- -- -- -- -- -- -- -- --
Tensile Strengh, psi 3620 3680 3730 3880 3790 3830 3720 4200 4220 4260
4290
Elongation, % 200 233 295 227 189 238 325 94 146 111 155
Tear Resistance, ft- 1118 1102 1008 1119 1106 1059 -- -- -- -- --
lbs/inch
Taber
Abrasion, g --
-- -- -- -- --
-- -- -- -- --
loss
Static decay +5,000 0.15 0.17 0.13 0.13 0.13 0.13 -- -- -- -- --
volts, sec
Static decay
-5,000 0.18
0.18 0.14 0.14
0.15 0.14 --
-- -- -- --
volts, sec
Surface
Resistivity,
1.6E+11
1.9E+11
7.8E+10
2.3E+11
2.2E+11
1.9E+11 -- --
-- -- --
ohms
Surface (12) -- -- -- -- -- -- -- -- -- -- --
__________________________________________________________________________
(1) Poly(tetramethylene adipate) glycol with 59% hard segment
(2) Poly(tetramethyleneadipate) glycol with 45% hard segment
(3) Poly(tetramethylene ether) glycol with 62% hard segment
(4) Poly(tetramethylene ether) glycol with 43% hard segment
(5) Poly(oxyethylene) glycol with 36% hard segment
(6) Polypropylene homopolymer
(7) Polypropylene homopolymer
(8) Maleic anhydride functionalized polypropylene
(9) PEGgrafted acrylic copolymer
(10) Copolyester
(11) Copolyamide
(12) Surfaces of molded plaques were judged for delamination (del), v
(very), sl (slight), sev (severe).
As apparent from the examples, good properties such as impact resistance,
tear resistance, good abrasion resistance, and the like were obtained
indicating good compatibilization of the blend of thermoplastic
polyurethane and polypropylene. Moreover, good static decay properties
were also obtained.
While in accordance with the patent statutes the best mode and preferred
embodiment has been set forth, the scope of the invention is not limited
thereto, but rather by the scope of the attached claims.
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